Surfactant mixtures



United States Patent I 3,303,137 SURFACTANT .MIXTURES George L.Broussalian, Overland, M0., assignor to Monsanto Company, a corporationof Delaware No Drawing. Filed Oct. 8, 1963, Ser. No. 314,648 9 Claims.(Cl. 252-152) The present invention relates to mixtures of surfaceactive agents having surprisingly effective general surface activeproperties. More particularly, this invention relates to novel mixturescontaining certain (a) vicinal acylamido higher alkyl sulfonates, (b)beta-ethylenically unsaturated higher alkene sulfonates, and (0)betamonohydroxy higher alkyl sulfonates, which mixtures aresynergistically effective with respect to at least several of theirimportant surface active properties.

Vicinal acylamido higher alkyl sulfonates such as those having thestructure illustrated by Formula 1:

(i H $03M wherein R and R are either hydrogen or alkyl radicals and thetotal (combined) number of carbon atoms in R plus R is from about 8 toabout 22, R" is an alkyl radical containing at most about '6 carbonatoms and M is either an ammonium, alkali metal, or alkaline earth metalcation; are excellent general purpose surfactants as well as excellentlime soap dispersants. One of the preferred processes for manufacturingsuch valuable Vicinal acylamido higher alkyl sulfonates involves thecontrolled interreaction of an appropriate olefin with sulfur trioxideto form, initially, a beta sultone, in accordance with Equation I:

H H H H RC=O-R+SO3 R(])-(I)R' OS0a The beta sultone can then be reactedwith an appropriate nitrile to yield a 2-dioxy-1,2,5-oxathiazine whichin turn can be hydrolyzed and then neutralized with an aqueous base toform the desired sulfonate:

One significant problem encountered by those who intend to manufacturethe vicinal acylamido higher alkyl sulfonate materials via sucholefin-SO -nitrile processes relates to the fact that, invariably inthese processes, a significant amount of by-product beta-hydroxy higheralkyl sulfonate material is also formed. These betahydroxy higher alkylsulfonates have structures such as those illustrated by Formula 2:

SOsM Depending upon the actual conditions experienced in conducting .theabove-described process, the amount of such by-aproduct beta-hydroxysulfonate material often ranges from about 2 to 5 weight percent toabout 50 weight percent, or even more, based on the weight of Vicinalacylamido higher alkyl sulfonate produced in the same process. Thisbeta-hydroxy sulfonate material is generally a very poor surfactant.Consequently, in order to optimize the surfactant properties of theirpreferred Vicinal acylamido higher alkyl sulfonate products, potentialmanufacturers of Vicinal acylamido higher alkyl sulfonates Who intend toutilize such olefin-SO -nitrile processes (particularly when they useprocess conditions that result in the formation of, for example, atleast about 10 weight percent of the by-product beta-hydroxy sulfonatematerial) would have to either (a) remove a large proportion of thebeta-hydroxy sulfonate material from the process mixture (i.e., purifythe viciual acylamido alkyl sulfonate) or (b) somehow enhance thesurfactant properties of the process mixture (of viciual acylamidohigher alkyl sulfonate with beta-hydroxy higher alkyl sulfonate). Fromthe standpoint of economics, this latter approach would be preferred,provided an inexpensive procedure could be made available in which thesurfactant properties of such mixtures can be enhanced. The detractingeffect by the beta-hydroxy sulfonate material on the generally excellentsurfactant properties of the Vicinal acylamido sulfonates can beappreciated from the fact, for example, that in a given standard testfor detergency in which cotton fabrics are washed under controlledconditions in an aqueous solution containing a given concentration ofthe surfactant material, the use of a mixture consisting of about weightpercent of sodium 2-acetamido-l-hexadecyl sulfonate and about 20 weightpercent of sodium Z-hydroxy-l-hexadecyl sulfonate resulted in a cleaningor detergency value of only 95, while pure sodium acetamido-l-hexadecylsulfonate gave a detergency value of 110.

It is an object of the present invention to provide surfactantcompositions containing at least one of the abovedescribed viciualacylamido higher alkyl sulfonates plus an amount of one of theabove-described beta-hydroxy higher alkyl sulfonates which wouldordinarily be sufficient to detract from the surfactant properties ofthe vicinal acylamido sulfonate material (practically any amount of thebeta-hydroxy material detracts to at least some extent) and a thirdsurfactant material, the presence of which overcomes the detractingeffect of the betahydroxy sulfonate material on the surfactantproperties of the composition.

The above, as well as other objects of this invention, can beaccomplished 'by incorporating into the mixture (of Vicinal acylamidoand beta-hydroxy sulfonates) an effective amount of a beta-ethylenicallyunsaturated higher alkene sulfonate such as one of those illustrated byFormula 3: v

(3) HIV wherein M has the same meaning as in Formula 1, above, and thesignificance of R and R will be described below. Although, in someinstances the use of as little as about 5 weight percent (or even less)of the unsaturated material (based on the total combined weight of theacylamido and hydroxy sulfonates) in the mixture can overcome thedetracting effect of the beta-hydroxy sulfonate, generally at leastabout half as much betaunsaturated material as the amount ofbeta-hydroxy material in the mixture should be utilized therein, When atleast this amount is utilized, particularly when amounts of beta-hydroxymaterial up to about 20 Weight percent, based on the total combinedweight of viciual acylamido sulfonate and beta-hydroxy sulfonatematerial, are present in the surfactant mixtures, the beneficialsynergistic properties of the resulting mixture are most evident; thegeneral surfactant properties of the resulting mixture beingsurprisingly better than those of any of the individual components ofthe resulting mixture alone. However, the beneficial effect of the betaunsaturated material can generally be noted when as little as about 20weight percent (based on the weight of beta-hydroxy sulfonate materialin the mixture), and sometimes even smaller amounts, of the betaunsaturated material is present therein; particularly in mixturescontaining larger amounts of the beta-hydroxy material. :It ispreferred, however, that the beta unsaturated material be present in thesurfactant mixtures of the present invention in amounts at least equalto those of the beta-hydroxy material therein. Stated otherwise, thesurfactant mixtures of this invention generally contain from about 40'to about 98 (preferably from about 50 to about 90) weight percent of oneor more vicinal acylamido sulfonates; from about 1 to about 30 (and moreusually from about to about 20) weight percent of one or more of thedetrimental beta-hydroxy sulfonates described above; and from about 0.5to about 30 (perferably from about 5 to about 20) weight percent of oneor more of the above-described beta-ethylenical unsaturated sulfonates.These weight percentages are based only upon the combined weight ofthese three types of sulfonates in the surfactant mixtures. It will beunderstood that these three sulfonates are not necessarily the onlycomponents in the surfactant mixtures of the present invention.

In the novel surfanctant mixtures of the present invention, generallythe vicinal acylamido sulfonates will be present in greater amounts thaneither of the other classes or types of surfactants. Thus, the weightratio of the vicinal acylamido sulfonates to beta-monohydroxy higheralkyl sulfonates, respectively, in these surfactant mixtures can be fromabout 20 or more to 1, to about 2: 1, and is generally from about 15:1to about 4:1, while the weight ratio of the vicinal acylamido sulfonatesto beta-ethylenically unsaturated higher alkene sulfonates,respectively, therein is generally from about 40 or more to l, to about5:1, and is preferably from about 15:1 to about 4:1.

As it was stated hereinbefore, the vicinal acylamido sulfonate materialsthat have been found to be useful in the practice of the presentinvention are those having the formula H SOaM wherein R and R are eitherhydrogen or alkyl radicals. The total (combined) number of carbon atomsin R plus R should be from about 8 to about 22, and is preferably fromabout to about 16 carbon atoms. It is also preferred that one of R or Rbe hydrogen, and still further preferred that R and/or R besubstantially straight chain in character, rather than branched to anyconsiderable extent. R" in these materials should be an alkyl radicalcontaining at most about 6 carbon atoms, and is preferably an alkylradical that contains from 1 to 3 carbon atoms. Typical non-limitingexamples of some of the vicinal acylamido sulfonate materials that canbe advantageously utilized in the practice of this invention includesodium 2-acetamido-n-hexadecane-1- sulfonate, potassium 1-propionamido ntetradecane-2- sulfonate, magnesium Z-butyramido-branched dodecane (froma-tetrapropylene)-1-sulfonate, ammonium6-acetamido-n-hexadecane-7-sulfonate, sodium 2-acrylarnidon-octadecane-l-sulfonate, sodium2-fl-methoxy-propionamido-hexadecane-l-sulfonate, sodium9-acetamido-n-do- 4 decane-lO-sulfonate, potassium2-(a-fl-dichloropropionamido)-n-hexadecane-l-sulfonate, and the like.

Note that in he compounds represented by Formula 1, above, M can beammonium, an alkali metal cation (such as Na, K, Li, Rb, Cs, and Fr), oran alkaline earth metal cation (such as Mg, Ca, Ba, Be, Sr, and Ra).Alkali metals, and particularly Na and K are preferred, however.

The beta-ethylenically unsaturated higher alkene sulfonates that areuseful in the practice of the present invention are preferably onlymono-unsaturated, and have the formula (3) III SOaM R"'o=ooR wherein R'and R are either hydrogen or alkyl radicals. The total (combined) numberof carbon atoms in R plus R should be from about 7 to about 21, and

dium 2-n-dodecene-l-phenyl-l-sulfonate,

is preferably from about 9 to about 15 carbon atoms. It is alsopreferred that either R or R be hydrogen, and still further preferredthat R and/or R be sub stantially straight chain in character, ratherthan branched to any significant extent.

These beta-ethylenically unsaturated higher alkene sulfonates can bemanufactured by sulfonating at very low temperatures (i.e., 0 C.) thecorresponding olefin with less than about 1.5 moles of sulfur trioxideper mole of olefin while the olefin is dissolved in a non-reactivesolvent; subsequently raising the temperature of the resulting reactionproduct to above about 20 C.; and then neutralizing the resultingsulfonic acid product. This method yields a mixture of sulfonates,including the desired beta-unsaturated sulfonate, which can be isolatedfrom the reaction product fairly readily by well-known separating andpurifying techniques.

It will be understood that generally the olefinic raw materials fromwhich these beta-ethylenically unsaturated sulfonates are made willcontain from a trace up to several weight percent or more of di-olefinicmaterials, depending upon the method of their manufacture. Thus, thesulfonates derived therefrom can contain up to several weight percent ofdi-functional material without detracting from the benefits that canresult from practicing this invention.

Typical, non-limiting examples of the beta-ethylenically unsaturatedhigher alkene sulfonates that are useful in the successful practice ofthe present invention include sodium 2-n-hexadecene-l-sulfonate, sodium2-n-dodecenel-sulfonate, magnesium 2-n-tetradecene-1-sulfonate,sodium-2-n-octadecene-l-sulfonate, potassium Z-(branched)pentadecene-l-sulfonate, ammonium 2-n-octaclecene-lsulfonate, ammonium2-n-pentadecene-l-sulfonate, sosodiu-rn 2-npentadecene 3 sulfonate,potassium 3 n heptadecene-Z-sulfonate, lithium2-n-octadecene-4-sulfonate, ammonium l-n-hexadecene-2-sulfonate, calcium3-n-heptadecene-Z-sulfonate, potassium 2-dodecene-l-sulfonate, sodiuml-(branched, from propylene) tridecene-l-sulfonate, sodium2,9-n-octadecadiene-l-sulfonate, potassium 9-n-octadecene-1Lsulfonate,solium l-n-octadecene-B-sulfonate, sodium 4-n-hexadecene-3-sulfonate,magnesium 2-n-dodecene-l-sulfonate, ammonium 2-n-dodecene-1-sulfonate,rubidium Z-n-pentadecene-l-sulfonate, sodium 2-n-octadecene-l-sulfonate, sodium 6-n-octadecene-5-sulfonate, sodium6-phenyl-1-n-pentadecene-3-sulfonate, and the like.

The beta-monohydroxy higher alkane sulfonates that are present in thesurfactant compositions of the present invention are those having theformula H S 03M wherein R, R and M have the same meaning in Formula 2 asthey do in Formula 1, above. Since the beta-hydroxy higher alkylsulfonate materials with which this invention is concerned are thosewhich would ordinarily be by-products in processes for the manufactureof the vicinal acylamido sulfonates described above, it will beappreciated that the beta-hydroxy sulfonates of the present inventioninclude all of those that can be made from olefins which, in turn, canbe used to prepare the vicinal acylamido higher alkyl sulfonatesdescribed above. The mixtures of sulfonates of this invention, however,can be made by simply admixing the various, relatively pure individualsulfonates, if desired.

In view of the problems described above, the surfactant compositions ofthe present invention will ordinarily be prepared by simply physicallyintermixing the desired amount of beta-ethylenically unsaturated alkenesulfonate with the mixture or blend containing vicinal acylamido alkanesulfonate plus beta-hydroxy alkane sulfonate. Each of these individualsurfactants is a solid material under ambient conditions. So, also, aremixtures of the relatively pure materials. Consequently, they can besimply blended together in any conventional mixing or blending equipmentdesigned to handle solid, particulated material. If desired, thesurprisingly elfective surfactant compositions of this invention canalso be manufactured by simply mixing together the individual surfactantmaterials; either in the dry, solid state, in water to form a slurry orsolution that can be dried to yield such dry, solid compositions, or inwater at end-use amounts to form immediately useful surfactantsolutions.

The mixtures of surfactants of this invention can be shipped, stored andhandled in the dry solid state if desired. They can :be particulated(i.e., powdered, flaked, or granular) and can also be utilized in theform of a solid mass such as a bar, pellet, or table if desired.Compositions containing these mixtures can also advantageously containany other material that can conventionally be employed in detergentcompositions. For example, they can also contain builders such as thewater-soluble alkali metal phosphates, polyphosphates, sulfates,carbonates, bicarbonates, and the like, all of which builders areWell-known in the detergent art. They can also contain other compatiblesurface active materials such as the well-known anionic, nonionic, andamphoteric surfactants, although generally, for best results, when themixtures of this invention are utilized in conjunction with still" othersurface active agents, the mixtures of this invention make up at leastabout 50 and preferably at least about 70 weight percent of the totalamount of organic surfactants present in these compositions.

Example 1 Into a conventional glass lined reaction vessel fitted with anexplosion proof stirring motor and an impeller type stirrer are charged2000 parts by weight of acetonitrile, 500 parts of chloroform, and 200parts of l-nhexadecene which is a mixture of a-olefins containing fromabout 12 to about 20 carbon atoms, the average chain length of saidolefins being about C Over a period of about 1 hour, While thetemperature of the resulting mixture is maintained at about l5 C., 100parts of liquid sulfur trioxide are added to the mixture while violentstirring is maintained. After the addition of the sulfur trioxide, thereaction mixture is stirred for an additional 30 minutes. Then thereaction mixture is warmed under vacuum to about 50 C. to evaporate theexcess acetronitrile and chloroform solvents. The product that remainscontains about 80 weight percent of 2- dioxy 3,4 dihydro 4 n tetradecyl6 methyl- 1,2,5-oxathiazine (a so-called inner anhydride), a few weightpercent of 2-hydroxy-n-hexadecane-1-sulfonic acid, and about 16 weightpercent of hexadecane B-sultone.

This residue is then stirred into about 10,000 parts of hot (ca. 90 C.)water, to which is then added a sufiicient amount of a 50 weight percentaqueous solution of sodium hydroxide to neutralize the aqueous solutionto a pH of 8. When this neutralized solution is then cooled to about 0C., crystals settle out of the aqueous mixture and are removed byfiltration and subsequently dried to yield a product containing aboutWeight percent of sodium 2-acetamido-1-n-hexadecane sulfonate (i.e.,average chain length=C and about 20 weight percent of sodiumZ-hydroxy-l-n-hexadecane sulfonate (i.e., average chain length=C Typicalsurfactant properties of this type of product are given in the followingtables, under the designation of product from Example I.

TABLE I.EVALUATION AS LIME SOAP DISPERSANT Sample No. Sample Tested 1Rating Control (soap) 10 Pure sodium Z-acetamido-n-hexadecane-1- 1-2sulfonate (average Cm). Pure sodium 2-hydroxy-n-hexadecane-l- 8sulfonate (average 010). Pure sodium 2-n-hexadecene-l-sulfonate 4 80%sodium Z-acetamido-n-hexadecane-l-sul- 4-5 fonate, 20% sodium2-hydroxy-n-hexadefined-sulfonate (product from Example 6 50% sodium2-acetamido-n-hexadecane-l-sul- 6 fonate, 50% sodiumZ-hydroxy-n-hexadecanal-sulfonate.

50% sodium 2-n-hexadeeene-l-sulfonate, 50% 7 sodium2-hydroxy-n-hexadecane-l-sulfo- Lime soap dispersantstested as a 15weight percent blend of the dispersant or dispersant mixture with weightpercent of sodium coco soap.

Sample number 10, above, was prepared by blending into a mixture such asthe product from Example 1, above, an amount of fairly pure sodium2-n-hexadecene-1-sulfonate (made from a mixture of a-olefins having anaverage chain length of approximately 16 carbon atoms) equal to theamount of 2-hydroxy material already present in the mixture.

The lime soap dispersant test is one that involves the measurement ofthe relative stickiness of lime soap scum or curds. Lime soap curds arethose that form at the surface of hard water after a soap has beendissolved therein. In addition to distributing the curd through theaqueous system, effective lime soap dispersants decrease or minimize thestickiness of the lime soap curds. In the test, which is conducted at atemperature between 30 and 35 C., 250 parts per million hard water(calculated as CaCO having a CazMg ratio of 2:1 is utilized. Five mls.of a 1 weight percent soap solution (or soap-lime soap dispersant blend)are shaken vigorously in a 50 ml. test tube. Then the resulting foam isimmediately stirred slowly into 500 mls. of the hard water in a 600 ml.beaker. After all of the foam is quenched and the solution has stoodundisturbed for 2 hours, the amount and particle size of scum, orsuspended lime soap curd, are observed and rated in comparison with soapalone and a standard soap-lime soap dispersant composition. Soap gives alow rating of 10, while the standard lime soap dispersed composition israted 3 in a test such as that just described.

TABLE -II.-CO,TTON FABRIC DETERGENCY TEST Sample No. Detergency Control(sodium dodecylbenzene sulfonate from tetrapropylene) 107 2 107 3 84 4108 5 102 6 98 7 95 8 106 9 107 10 115 11 112 1 In 300 p.p.m. hardwater. Test described by Jay C. Harris 3111 lggalleuation of SurfaceActive Agents ASTM Bulletin,

2 Sample numbers correspond to those in Table 1, above.

TABLE IIL-ROSS-MILES LATHER TEST Foam Height (cm) Sample No.

Immediate 5 Minutes Control (sodium dodecylbenzene sulfonate-fromtetrapropylene) 19. 4 19. 3 2 21 20. 5 3 2.6 19. 7 19. 6 19 15 15 7 1812 21 20 21 20. 5 22 21 21. 5 21 1 Test run at 50 C. 2 Same samples,according to Sample No. as in Table I.

TABLE 'IV.HA1ND DISHWASHING TEST 1 Same samples, according to Sample No.as in Table I.

'The hand dishwashing test of Table IV, above, involves the Washing byhand of nine-inch dinner plates which are pre-soiled with oneteaspoonful each of a synthetic soil mixture consisting of 75 weightpercent of shortening and weight percent of flour. Washing of the platesis performed (using a dishcloth to remove the synthetic soil) in 4liters of water having an initial temperature of about 50 C. andcontaining 0.075 weight percent of the surfactant or surfactant mixturebeing tested. The number of plates washed (for the data above) isdetermined by the number of plates which can be cleaned in the norm-a1fashion by the time the lather on the surface of the dishpan has brokento the extent that less than half of the surface remains covered withlather. The manipulative procedures of this test are described ingreater detail in the Proceedings of the 43rd Annual Meeting of theChemical Specialties Manufacturers Association, December, 1956;Procedure No. 3, page 191.

TABLE V.WETTI NG TIME (DRAVl'JS-CLARIQS O'N) Sample No. Time (seconds) 275 3 250 4 5 75 6 7 150 -8 6O 9 6 0 10 20 11 25 1 Concentration ofsurfactant or surfactant mixture in distilled Water is 0.125 weightpercent.

2 Same samples, according to Sample No. as in Table I.

The foregoing evaluation data illustrate the surprising synergisticaction that is exhibited by the surfactant compositions of the presentinvention. Note that, generally, the surfactant properties of thecompositions of this invention are excellent, while in each test, thebinary mixture (vicinal acylamido sulfonate plus beta-hydroxy material)is significantly poorer than the compositions of this invention.Similarly, in several of the foregoing tests the compositions of thepresent invention are significantly better than the relatively purebeta-unsaturated materials.

In order to utilize the non-aqueous surfactant compositions of thisinvention as general purpose surfactants, they need merely be dissolvedin effective amounts, generally at concentrations of at least about0.005 weight percent or more (up to as much as about 20 weight percentor the limits of their solubility; or even higher if slurries aredesired to be used) in water.

Although, in the foregoing example and tests, data for mixtures madefrom a-n-hexadecene are given, it will be understood that similarcomparative data result when data for other mixtures of the presentinvention are similarly compared.

What is claimed is:

1. A detergent composition comprising a mixture of (a) from about 40 toabout 98 weight percent, based on the weight of said mixture, a vicinalacylamido sulfonate having the Formula 1 wherein R and R are selectedfrom the group consisting of alkyl radicals and hydrogen; the totalnumber of carbon atoms in R plus R being from about 8 and about 22; M isa cation selected from the group consisting of alkali metal, alkalineearth metal, and ammonium cations, and R" is an alkyl radical containingfrom 1 to 6 carbon atoms; (b) from about 1 to about 30 weight percent,based on the weight of said mixture, a beta-hydroxy sulfonate having theFormula 2 wherein R, R' and M have the same meaning .as in said Formula1; and (c) from about 0.5 to about 30 weight percent, based on theweight of said mixture, of a betaethylenic-ally unsaturated sulfonatehaving the Formula 3 wherein M has the same meaning as in said Formula1, and R and R are selected from the group consisting of alkyl radicalsand hydrogen, the total number of carbon atoms in R-l-R from about 7 toabout 21.

2. A composition as in claim 1, wherein the amount of saidbeta-ethylenioally unsatunated sulfonate is equal to at least about onehalf of the amount of said betahydroxy sulfonate in said composition.

3. A detergent composition which contains a mixture wherein R and M arethe same as R and M, respectively, in said vicinal acylamido sulfonate;(c) a beta-unsaturated sulfonate having the Formula 3 wherein M has thesame meaning as in said Formula 1 and R is an alkyl radical containingfrom about 9 to about 15 carbon atoms; and the weight ratio of saidvicinal acylamido sulfonate to said beta-unsaturated sulfonate,respectively, in said composition being from about 40:1 to about :1, andthe weight ratio of said vicinal acylamido sulfonate to saidbeta-hydroxy sulfonate, respectively, in said composition being fromabout 15:1 to about 4: 1.

4. A detergent composition as in claim 3, wherein said R is a straightchain alkyl radical and said M is sodium.

5. A detergent composition as in claim 3, wherein said R is a straightchain alkyl radical and said M is potassium.

6. A detergent composition containing from about 40 to about 98 weightpercent of sodium 2-acetamido-hexadecane-l-sulfonate, from about 0.5 toabout 30 weight percent of sodium 2-hexadecene-l-sulfonate, and fromabout 1 to about 30 weight percent of sodium 2-hydroxyhexadecane-l-sulfonate.

7. An aqueous detergent solution containing from about 0.005 to about 20weight percent of a synergistically effective surfactant mixture, saidmixture cont-aining (a) from about to about weight percent of an alkalimetal vicinal acylamido higher alkyl sulfonate compound 'wherein theacyl group contains from 1 to 4 carbon atoms and the higher alkylradical contains from about 12 to about 18 carbon atoms and isunsubstituted except for the acylamido and sulfonate groups, (b) fromabout 5 to about 20 weight percent of an alkali metal beta-ethylenicallyunsaturated alkene-l-sulfonate, wherein the alkene radical contains fromabout 12 to about 18 carbon atoms and is unsaturated at only the2-position, and (c) from about 5 to about 20' weight percent of analkali metal 2-hydroxy alkyl sulfonate, wherein the alkyl radicalcontains from about 12 to about 18 carbon atoms.

8. An aqueous detergent solution as in claim 7, wherein said higheralkyl, said alkene, and said alkyl radicals are a mixture of straightchain radicals containing from about 10 to about 24 carbon atoms; saidmixture having an average chain length of from about 12 to about 18carbon atoms.

9. An aqueous detergent solution as in claim 7, wherein said alkalimetal is sodium.

References Cited by the Examiner UNITED STATES PATENTS 1,932,180 10/1933Guenther et a]. 2,061,619 11/1936 Downing et al. 252353 XR 2,843,5507/1958 Stayner 252152 2,857,370 10/19'58 Sundberg 252-152 XR 3,187,0266/1965 Klass 260'401 OTHER REFERENCES Folk et al.: J. Am. Oil ChemistsSoc., vol. 35, pp. 171-176 (1958).

LEON D. ROSDOL, Primary Examiner.

ALBERT T. MEYERS, Examiner.

S. E. DARDEN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N00 3,303,137 February 7 1967 George L Broussalian that error appears in theabove numbered pat- It is hereby certified d that the said LettersPatent should read as ent requiring correction an corrected below.

Column 9, line 5, vicinal acylamido sulfonat 9, lines 6 to 11, for thaMO read 80 M Signed and sealed this 28th day of November 1967.,

(SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, J1.

Commissioner of Patents Attesting Officer

1. A DETERGENT COMPOSITION COMPRISING A MIXTURE OF (A) FROM ABOUT 40 TOABOUT 98 WEIGHT PERCENT, BASED ON THE WEIGHT OF SAID MIXTURE, VICINALACYLAMIDO SULFONATE HAVING THE FORMULA 1